Metal salts of polyhydroxyalkyldithiocarbamic acids and their preparation



yrectly, from the reaction, e.-"g., the salts MM July 10, 1945.

METAL SALTS OF POLYHYDROXYALKYL- DITHIOOARBAMIC 'ACIDS AND THEIRPREPARATION Madison Hunt, Claymont, not, assignor to E. I. du Pont deNemours & Company, Wilmington, Del., a-corporationof Delaware NoDrawing. Application March 4, 1944, Serial No. 525,121

7 Claims. (or. 260-211) This invention relates to metal salts 01'polyhydroxyalkyldlthiocarbamic acids and to their preparation.

This invention has as an object the production of new and usefulcompositions of matter. A further object is the preparation ofmetal-salts of polyhydroxyalkyldithiocarbamic acids. Other ob- Jectswill be apparent from the following description of the invention.

These objects are accomplished by the fol lowing invention wherein apolyhydroxyalkylamine having at least one hydrogen on the nitro gen isreacted in an alkaline medium with carbon bisulflde. The invention alsocomprises the products which may be obtained, directly or indiof theformula R-N0S l l wherein M is a metal of valence 2:, a: is an integerfrom 1 to 3, R is a polyhydroxyalkyl radical, i. e., an alkyl radicalhaving at least three hydrogens replaced by hydroxyls, and preferablythe radical of a reducing sugar, and R is hydrogen, hydrocarbon, oroxyhydrocarbon.

The more detailed practice of the invention is illustrated by thefollowing example, wherein parts given are by weight. There are,-ofcourse, manyforms of the invention other than this specific embodiment.

Example To a solution of 12.5 parts of sodium dissolvedin 600 parts ofabsolute ethyl alcohol is added 98 parts of N-methylglucamine. Themixture is stirred vigorously 'and 88 parts of carbon bisulfide is addeddrop-wise while maintaining a temperature of 25 C. The reaction mixtureis stirred for three hours and is then filtered and the product washedwith absolute alcohol. Recrystallization of the crystalline solid fromaqueous ethyl alcohol yielded 85 parts of the monomrdrate of the sodiumsalt of N-methyl-N-sorbityldithiocarbamic acid melting at' l53-l55 C.Analysis: Calculated for CsH1sNO5S2NaH20: S, 20.57; E20, 5.78. Found: S,20.02; H2O (loss of weight on drying) 5.30.

The metal salts of the polyhydroxyalkylclithiocarbamic acids can beprepared by treating an aqueous solution of an alkali metal salt of apolyhydroxyalkyldithiocarbamic acid prepared as described above with anaqueous solution of a salt 01' the desired metal. Thus copper salts ofpoly-' hydroxyalkyldithiocarbamic acids are produced when an alkalimetal (e. g., soclium) salt of the polyhydroxyalkyldithiocarbamic acidis reacted with an aqueous solution of a copper salt, e. g., coppersulfate. The silver, gold, cadmium, zinc, tin, arsenic, antimony,bismuth, lead, and other heavy metal salts are preferred since they areless soluble in aqueous solutions and are therefore more readilyprepared by double decomposition of solution of the sodium salt of thepolyhydroxyalkyldithiocarbamic acid and an appropriate soluble salt ofthe heavy metal. The acid may be prepared from a suitable heavy metalsalt, e. g., the lead salt, by passing hydrogen sultide throughan'aqueous suspension thereof, filtering oi! the lead sulfide andconcentratingthe aqueous solution, desirably in an inert atmosphere.Alkali metal, e. g., potassium and lithium,

I alkaline earth, e. g. magnesium, and earth metal,

,e. 3., aluminum, salts may be made from the aqueous solution of theacid and a carbonate or hydroxide of the metal.

Although the invention is illustrated by the metal salts ofpolyhydroxyalkyldithiocarbarnic acids obtainable from methylglucamine,it is applicable to polyhydroxyalkyldithiocarbamic acid salts ingeneral. Thus polyhydroxyalkylamines, other than methylglucamine, canbeused in the process of this invention. Examples of such amines are thoseobtainable by the hydrogenation of a monosaooharide in the presence ofammonia or a primary amine as described in U. S.

2,016,962, U. S. 2,016,963 and U. S. 2,193,433.

primary amines are the polyhydroxyalkylaminessuch as'trihydroxybutylamines, tetrahydroxyamylamines, pentahydroxyhexylaminesand their N-ethyl, N-butyl, N-hydroxethyl, N-phenyl, N-omethoxyphe'nyl,N-p-hydroxyphenyl, and N-ben- The hydroxyls are of course onzylderivatives. different carbons.

Other solvents may be used as media for the" preparation of thedithiocarbamic acid salts.

These include alcohols, such as methyl alcohol, thiocarbamic acidwherein the N-polyhydroxypropyl alcohol and isobutyl alcohol, and water.alkyl radical is that or a reducing sugar.

The temperature at which the reaction is gen- 2. A heavy metal salt ofan N-polyhydroxyalerally carried out is within the range 0 to 100 C.kyldithiocarbamic acid wherein the N-polyhy- However, it'ls convenientto operate at or near 5 droxyalkyl radical is that of a reducin sugar.

room temperature. 3. A heavy metal salt of an N-sorbityldithiovTheproducts of this invention are useful for carbamic acid.various-commercial purposes. They may be used 4. A heavy metal salt ofN,N-methyl-N-soras intermediates for the preparation of otherdebityldithi'ocarbamic acid.

rivatives of the polyhydroxyalkyl dithiocarbamic 10 5. Asalt ofNmethyl-N-sorbityldithiocarbamic acids, as pharmaceuticals and pestcontrol agents, acid.

e. g., bactericides, fungicides, insecticides, moth- 6. Process for thepreparation of metal salts proofing agents and as additive agents forelasof dithiocarbamic acids having on the nitrogen tomers. the radicalof a reducing sugar which comprises As many apparently widely differentembodiis reacting an amine having on the nitrogen at ments of thisinvention may be made without least one hydrogen and the radical of areducing departing from the spirit and scope thereof, it sugar withcarbon bisulfide in alkaline medium.

is to be understood that this invention is not 7. Process whichcomprises reacting N-methyllimited to the specific embodiments thereof,exglucamine with carbon bisulfide in alcoholic socept as defined in theappended claims. no dium ethylate solution.

What is claimed is: MADISON HUNT.

1. A metal salt of an N-p lyhydroxyalkyldi- CERTIFICATE or CORRECTION.Patent No 2,579,965. July 10, 1915.

MADISON HUNT.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correcti'onas follows: Page 2,second column, line 8, claim 1+, for ."N,N -methy1-N-sor "read-N-methyl-ll-sorand that the. said Letters Patent shouldbe readwith thiscorrection th'er ein that the same may'conform to the record of the casein the Patent Office.

Signed and sealed this 15th day or January, A. D. 19%. I

Leslie Frazer (See.1)' First Assistant Commissioner of Patents,

These include alcohols, such as methyl alcohol, thiocarbamic acidwherein the N-polyhydroxypropyl alcohol and isobutyl alcohol, and water.alkyl radical is that or a reducing sugar.

The temperature at which the reaction is gen- 2. A heavy metal salt ofan N-polyhydroxyalerally carried out is within the range 0 to 100 C.kyldithiocarbamic acid wherein the N-polyhy- However, it'ls convenientto operate at or near 5 droxyalkyl radical is that of a reducin sugar.

room temperature. 3. A heavy metal salt of an N-sorbityldithiovTheproducts of this invention are useful for carbamic acid.various-commercial purposes. They may be used 4. A heavy metal salt ofN,N-methyl-N-soras intermediates for the preparation of otherdebityldithi'ocarbamic acid.

rivatives of the polyhydroxyalkyl dithiocarbamic 10 5. Asalt ofNmethyl-N-sorbityldithiocarbamic acids, as pharmaceuticals and pestcontrol agents, acid.

e. g., bactericides, fungicides, insecticides, moth- 6. Process for thepreparation of metal salts proofing agents and as additive agents forelasof dithiocarbamic acids having on the nitrogen tomers. the radicalof a reducing sugar which comprises As many apparently widely differentembodiis reacting an amine having on the nitrogen at ments of thisinvention may be made without least one hydrogen and the radical of areducing departing from the spirit and scope thereof, it sugar withcarbon bisulfide in alkaline medium.

is to be understood that this invention is not 7. Process whichcomprises reacting N-methyllimited to the specific embodiments thereof,exglucamine with carbon bisulfide in alcoholic socept as defined in theappended claims. no dium ethylate solution.

What is claimed is: MADISON HUNT.

1. A metal salt of an N-p lyhydroxyalkyldi- CERTIFICATE or CORRECTION.Patent No 2,579,965. July 10, 1915.

MADISON HUNT.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correcti'onas follows: Page 2,second column, line 8, claim 1+, for ."N,N -methy1-N-sor "read-N-methyl-ll-sorand that the. said Letters Patent shouldbe readwith thiscorrection th'er ein that the same may'conform to the record of the casein the Patent Office.

Signed and sealed this 15th day or January, A. D. 19%. I

Leslie Frazer (See.1)' First Assistant Commissioner of Patents,

